低温水热法制备ZnS:Co+Cr纳米晶及其光学性能研究

采用低温水热法制备出3-巯基丙酸(MPA)修饰的ZnS:Co+Cr纳米晶. 利用X射线衍射仪、粒度分析仪、透射电镜、紫外-可见分光光度计、荧光分光光度计和XPS能谱仪等对ZnS:Co+Cr纳米晶的结构、形貌、粒径分布和发光性能进行了表征. 结果表明: 合成的ZnS:Co+Cr纳米晶有较好的单分散性, 平均粒径为9.3 nm, 均为立方闪锌矿结构; ZnS:Co+Cr纳米晶的吸收边位于320 nm处, 并在728 nm处出现Co²⁺的特征吸收峰; 当Cr²⁺浓度为0.75at%, 水热反应温度为160℃时, ZnS:Co+Cr纳米晶PL峰最强; XPS能谱表明Cr²⁺部分被氧化成Cr³⁺。     

ZnS/PVA纳米复合薄膜的制备与表征

采用提拉真空干燥的方法制备出以石英玻璃为基板的ZnS/PVA纳米复合薄膜.ZnS/PVA纳米复合溶胶是通过直接混合法将ZnS纳米粒子与聚乙烯醇(PVA)高分子材料水溶液直接混合制备得到.ZnS纳米粒子由微乳液法制备得到.利用透射电子显微镜(TEM)和X射线衍射(XRD)分析表征了ZnS纳米粒子的微观形貌和晶型,TEM结果表明C12H25SH与Zn2 的比例越大,ZnS粒子的粒径越小且在PVA中的分散越好,当C12H25SH/Zn2 的比例为8∶1时,ZnS纳米粒子的粒径为50 nm,呈球状;XRD分析表明,PVA中ZnS纳米粒子具有类似于立方β-ZnS晶相.用紫外-可见(UV-VIS)吸收光谱和荧光光谱(PL)对其光学性能进行了表征,结果表明随着C12H25SH/Zn2 的摩尔比从4:1增长到8:1,ZnS/PVA纳米复合薄膜的吸收峰的强度逐渐增强,峰位也逐渐向短波长方向偏移.在280 nm下激发,PL中出现了峰位位于365 nm处的荧光发射峰;并且发现随着C12H25SH/Zn2 摩尔比从2:1增大到8:1,在C12H25SH/Zn2 摩尔比为4:1时,荧光发射峰的强度相对较大, 其余的荧光发射峰蓝移并且强度增大,表现出较为明显的量子尺寸效应;当C12H25SH/Zn2 摩尔比较大时,出现了低能发光(450 nm～467 nm)的现象.     

纳米ZnS:Cd的光致发光特性

研究了Cd^2 掺杂的ZnS纳米晶的光致发光特性,结果表明,当Cd的掺杂量较低时（≤5%,摩尔分数）,ZnS纳米晶试样的荧光强度显著提高,Cd的掺杂量为0.5%时,掺杂试样的相对荧光强度约为未掺杂试样的5倍,发射光谱明显宽化,随着Cd含量的提高,试样的激发光谱（350nm→488nm）和发射光谱（由蓝→绿→红）红移,当Cd含量≥5%时,其发射光谱与CdS纳米晶一致,但荧光强度比CdS纳米晶高。XRD分析显示,掺杂试样的晶格结构由Cd的掺杂量决定。     

木质纤维素基纳米复合材料对Pb~(2+)、Cd~(2+)的吸附研究

以原位插层共聚法制备木质纤维素-g-丙烯酸/丙烯酰胺/蒙脱土(LNC-g-AA/AM/MMT)纳米复合材料,采用X射线衍射(XRD)、扫描电镜(SEM)对其结构进行表征。研究在金属离子初始浓度、吸附时间、吸附温度、pH值等不同吸附条件下,LNC-g-AA/AM/MMT纳米复合材料对Pb2+、Cd2+吸附性能的影响。结果表明,当Pb2+、Cd2+初始浓度分别为0.04和0.06mol/L,吸附时间分别为120和60min,吸附温度分别为40和30℃,pH值为5.5时,LNC-g-AA/AM/MMT纳米复合材料对Pb2+、Cd2+的吸附量分别高达504.2和246.9 mg/g。整个吸附过程均符合Langmuir吸附等温线模型和伪二级动力学模型,且是个自发放热的反应过程。同时对最佳条件下吸附饱和的LNC-g-AA/AM/MMT纳米复合材料进行解吸研究,脱附率分别为93.4%和92.9%。     

沉淀法制备ZnS∶Cr纳米晶及其光学性能研究

以十二烷基苯磺酸钠和六偏磷酸钠作为分散剂,采用沉淀法制备了ZnS及不同掺杂浓度的ZnS∶Cr纳米晶。利用XRD和TEM对纳米晶物相和形貌进行了分析。结果表明,ZnS和ZnS∶Cr纳米晶均为立方闪锌矿结构,利用谢乐公式估算ZnS和ZnS∶Cr纳米晶平均粒径分别为2.1和2.2nm。TEM观察到纳米晶近似为球形,平均粒度为3nm左右,具有较好的单分散性且分布均匀。荧光光谱(PL)表明,纳米晶在420、440和495nm处有发射谱带,前两者被认为是S空位深陷阱发光,后者被认为是表面态或中心辐射复合发光。     

原位聚合法制备聚丙烯酸修饰的ZnS量子点

采用原位聚合法对ZnS量子点表面进行聚丙烯酸(PAA)的修饰。利用XRD、FTIR、TEM、TGA、荧光测试等对ZnS@PAA复合纳米粒子进行系列表征。XRD分析表明,修饰后的ZnS仍为立方晶相。FTIR和TGA结果证明,ZnS纳米粒子表面存在PAA。TEM结果表明,修饰后ZnS@PAA复合纳米粒子在去离子水中分散良好,其直径有所增加,约为28 nm,且呈较明显的核-壳结构。荧光测试发现,修饰PAA前后ZnS@PAA复合纳米粒子的发光特性没有发生明显改变。实验表明,经PAA修饰后,ZnS@PAA复合纳米粒子在水溶液中的分散性和稳定性得到提高,抗氧化性和荧光稳定性也得到了一定的增强。      

Mn~(2+)掺杂水溶性ZnS量子点的制备及其光致发光性能

采用共沉淀法,在3-巯基丙酸(MPA)为表面修饰剂下,成功制备出Mn2+掺杂水溶性ZnS量子点。利用X射线衍射仪、透射电子显微镜、紫外-可见吸收光谱仪和荧光分光光度计等表征方法研究了Mn2+掺杂剂及掺杂量对ZnS量子点的晶体结构、形貌和发光性能等的影响。结果表明,所得产物为ZnS立方型闪锌矿结构,样品呈不规则球形,粒径主要集中在9.7nm左右;在320nm激发下,Mn2+掺杂ZnS量子点出现两个发射波峰,分别位于587和637nm处,其中587nm处的发射波峰为ZnS表面态缺陷发光,而637nm处的发射波峰则属于Mn2+∶4T1-6A1能级特征发光。同时,利用红外吸收光谱对Mn2+掺杂水溶性ZnS量子点的形成机理进行了初步探讨。     

Y_2O_3∶Eu~(3+)纳米晶的尺寸调控与发光性能研究

以尿素为沉淀剂,柠檬酸为表面活性剂,通过水热法得到了非晶态的水合硝酸氧钇前驱体,进一步烧结处理后生成了立方相Y_2O_3纳米晶.利用X-射线衍射(XRD)、扫描电镜(SEM)、透射电镜(TEM)、红外光谱(FTIR)和荧光光谱(PL)分别对所得样品的相结构、形貌粒度、表面结构以及发光性能进行研究.结果表明:当烧结温度从600℃升高到900℃,Y_2O_3∶Eu~(3+)纳米颗粒的结晶性增强,并实现了粒径调控,由13.0 nm增加至27.9 nm.随着Y_2O_3∶Eu~(3+)纳米颗粒尺寸的增加,比表面积减小会导致发光离子附近的表面晶格缺陷降低,同时纳米晶表面吸附水、硝酸根以及柠檬酸根等杂质离子逐渐被去除,减少了荧光猝灭中心,从而有利于增强荧光发射强度以及延长荧光寿命.     

原位复合制备纤维素基CdS纳米复合材料及其表征

以微晶纤维素(MCC)为模板,氯化镉、硫化钠等为原料,在水的悬浮液中,用原位复合法制备了MCC/CdS纳米复合材料。对复合反应条件进行了初步研究,探讨了Cd2+浓度、Cd2+吸附时间及超声功率对复合反应的影响。研究表明,适当提高Cd2+吸附时间及超声功率有利于提高复合材料中硫化镉颗粒的复合量,Cd2+浓度对复合量的影响是显著的。应用X射线衍射(XRD),扫描电镜(SEM),红外光谱(FT-IR),光致荧光光谱(PL)对MCC/CdS复合材料进行了表征。结果表明,复合在微晶纤维素上的CdS颗粒大小均一,且均匀分布在微晶纤维素模板表面;制备的复合材料具有一定的荧光特性。     

MS(M=Cd或Zn)纳米粒子负载TiO_2纳米线的制备及可见光催化性能

以具有层状结构的钛酸盐纳米线、CdCl2或ZnSO4及硫代乙酰胺为原料,采用两步水热合成法制备了高温稳定的六方相CdS或低温稳定的立方相ZnS纳米粒子负载的TiO2纳米线复合材料。首先,CdCl2或ZnSO4与钛酸盐纳米线在水热条件下进行离子交换制得含Cd2+或Zn2+的钛酸盐纳米线;然后,在硫代乙酰胺溶液中于160℃下直接处理含Cd2+或Zn2+的钛酸盐纳米线就可获得负载有硫化物纳米粒子的TiO2复合纳米线。它们在酸浸后,TiO2纳米线的表面仍存在少量硫化物纳米粒子。通过测试酸浸后样品、纯TiO2纳米线和商用P25对亚甲基蓝水溶液的可见光催化降解实验结果证实,含CdS纳米粒子样品的光催化活性最高。     

Hydrothermal synthesis and optical properties of Eu(3+)-doped CaSnO3 nanocrystals

In this paper, CaSnO3:Eu3+ nanocrystals were prepared by hydrothermal synthesis method. The influence of different molar ratio of Ca:Sn on structure of CaSnO3:Eu3+ was investigated by using X-ray powder diffraction (XRD). Well-crystallized and phase-pure CaSnO3:Eu3+ particles of approximately 90 nm in size can be readily obtained at 900 degrees C. Furthermore, photoluminescence characterization of the Eu(3+)-doped CaSnO3 nanocrystals was performed and discussed. The emission peak situated at 618 nm showing prominent and bright red light is due to the 5D0-7F2 electric dipole transition. The excellent luminescence properties make it possible as a good candidate for PDP application.     

新型纳米ZrO2/聚酰亚胺复合超薄膜的制备表征及其介电性能

以油酸为有机配体,采用两相方法合成了油溶性的超小尺寸纳米晶体纳米ZrO₂（nano ZrO₂）,并对nano ZrO₂表面包覆的油酸改性使纳米晶体与聚酰胺酸（PAA）接枝,通过旋膜法热亚胺化后形成nano ZrO₂/聚酰亚胺（PI）复合超薄膜。利用TEM、XRD、FTIR和SEM等对nano ZrO₂及nano ZrO₂/PI复合超薄膜进行表征,并对nano ZrO₂/PI复合超薄膜的介电性能进行了探究。结果显示,nano ZrO₂尺寸均一（5.0 nm左右）,为锐钛矿晶型,其晶体结构和尺寸不受改性接枝影响。nano ZrO₂在复合超薄膜中分散良好。电学研究表明,复合超薄膜的介电性能受nano ZrO₂与PAA质量比及制膜热亚胺化温度的影响。当PAA∶ZrO₂质量比为2∶3、热亚胺化温度为320℃时,介电常数达到最大,几乎是纯PI薄膜的2倍。两相法-改性接枝-热亚胺化制备PI复合超薄膜的方法简单高效,能够避免无机粒子在PI基体内的团聚并提高介电性能,对于PI基复合薄膜的制备、应用及推广具有重要意义。     

Preparation and Tribological Behavior of BiIn/In_2O_3 Composite Dendritic Nanocrystals

BiIn/In2O3 composite dendritic nanocrystals were prepared by dispersing alloy droplets in paraffin oil. The morphology and structure of the alloy nanocrystals were characterized by transmission electron microscopy (TEM), X-ray photoelectron spectra (XPS), and X-ray powder diffraction (XRD). The composite nanocrystals have dendritic morphology, with an average diameter of 10 nm and lengths up to tens and even hundreds of nanometers. Tribological results indicate that the composite nanocrystals as oil additiv...     

具有催化与渗透汽化双功能的纳米TiO2和Al2O3填充复合膜性能

采用聚丙烯腈(PAN)中空纤维超滤膜作为支撑底膜,经戊二醛(GA)表面交联的聚乙烯醇(PVA)作为渗透汽化层,以及纳米TiO2或Al2O3填充的全氟磺酸树脂(PFSA)作为催化层,制备了催化与渗透汽化双功能复合膜,考察了其亲水性能、对乙酸乙酯塔顶粗酯的渗透汽化分离性能、催化酯化反应性能以及机械性能.实验结果表明:催化与渗透汽化双功能复合膜具有良好的亲水性和机械性能,渗透通量可达到179g/(m2.h),相对应的分离系数为95,渗透物中不含乙酸乙酯,同时可显著缩短酯化反应达到相同转化率的时间.     

Efficient doping and energy transfer from ZnO to Eu3+ ions in Eu(3+)-doped ZnO nanocrystals

Successful doping of Eu3+ ions into ZnO nanocrystals has been realized by using a low temperature wet chemical doping technique. The substitution of Eu3+ for Zn2+ is shown to be dominant in the Eu-doped ZnO nanocrystals by analyzing the X-ray diffraction patterns, transmission electron microscopy images, Raman and selectively excited photoluminescence spectra. Measurement of the luminescence from the samples shows that the excited ZnO transfers the excited energy efficiently to the doped Eu3+ ions, giving rise to efficient emission at red spectral region. The red emission quantum yield is measured to be 31% at room temperature. The temperature dependence of photoluminescence and the photoluminescence excitation spectra have also been investigated, showing strong energy coupling between the ZnO host and Eu3+ ions through free and bound excitons. The result indicates that Eu3+ ion-doped ZnO nanocrystals are promising light-conversion materials and have potential application in highly distinguishable emissive flat panel display and LED backlights.     

脉冲激光喷涂一步合成黑色二氧化钛复合涂层

为实现黑色纳米TiO₂有效负载, 提高实际应用能力, 本研究提出了脉冲激光溅射喷涂的方法。在石英玻璃基底上一步制备了非晶分子筛和金红石型TiO₂纳米晶的黑色复合涂层, 表征了复合涂层表面形貌, 测定了复合涂层粉末的光谱吸收性能、物相结构、化学价态以及光催化性能。研究结果表明: 涂层为2~5 μm球体堆积成的多孔结构, 在整个可见光区具有较强的吸收能力。脉冲激光溅射喷涂过程中, 分子筛高温熔融急冷转变为非晶态结构, TiO₂则由锐钛矿型转变为金红石型; 其中Ti⁴⁺离子部分被还原为Ti³⁺离子, 缩小了禁带宽度。脉冲激光溅射喷涂技术实现了黑色纳米TiO₂快速负载, 且在全光谱和可见光条件下仍表现出良好的光催化能力。     

Solvothermal synthesis of crystalline phase and shape controlled Sn(4+)-doped TiO2 nanocrystals: effects of reaction solvent

The Sn(4+)-doped TiO(2) nanocrystals with controlled crystalline phase and morphology had been successfully prepared through easily adjusting the solvent system from the peroxo-metal-complex precursor by solvothermal method. The Sn(4+)-doped TiO(2) nanocrystals were characterized by XRD, Raman, TEM, HRTEM, XPS, ICP-AES, BET, and UV-vis. The experimental results indicated that the Sn(4+)-doped TiO(2) nanocrystals prepared in the pure water or predominant water system trend to form rodlike rutile, whereas the cubic-shaped anatase Sn(4+)-doped TiO(2) nanocrystals can be obtained in the alcohol system. The growth mechanism and microstructure evolution of the Sn(4+)-doped TiO(2) nanocrystals prepared in the different solvent systems are discussed. The liquid-phase photocatalytic degradation of phenol was used as a model reaction to test the photocatalytic activity of the synthesized materials. It was found that sample Sn(4+)-doped TiO(2) prepared in 1-butanol showed the maximum photoactivity, which attributed to higher band gap, optimal crystalline phase and surface state modifications.     

Site-selective spectroscopy in Sm(3+)-doped sol-gel-derived nano-glass-ceramics containing SnO(2) quantum dots

Nano-glass-ceramics of composition 95SiO(2)-5SnO(2) doped with 0.4 Sm(3+) (mol%) were synthesized by the thermal treatment of precursor sol-gel glasses. Structural and luminescence measurements were carried out. The precipitated SnO(2) nanocrystals in the glass matrix constitute a wide bandgap quantum-dot system with size comparable to the bulk exciton Bohr radius. A site-selective excitation, by energy transfer from the semiconductor host, reveals that a fraction of the Sm(3+) ions are incorporated in the SnO(2) nanocrystals, whereas the rest remains in the silica glassy phase. An evolution in the Sm(3+) emission spectra has been observed when the SnO(2) nanocrystals are excited with different UV wavelengths, which has been ascribed to selective excitation of nanocrystal sets with predetermined size.     

Synthesis and characterization of nickel doped cadmium sulfide (CdS:Ni2+) nanoparticles

Nickel doped cadmium sulfide (CdS:Ni²⁺) nanocrystals were synthesized at three different pH values. Nanocrystalline state of nickel doped cadmium sulfide material was established using X-ray diffraction analysis. Peak broadening and peak shifts in the XRD spectra were caused by the replacement of Cd²⁺ with Ni²⁺. Particles size (～62 nm) and the morphology of the synthesized nanoparticles were established through SEM analysis. The TEM analysis further established the presence of nanostate with particles size of 35 nm. The EDS analysis confirmed the existence of Ni in all the three samples. Blue shift in the absorption region and increase in the bandgap to the larger value (3.72 eV) were attributed to the nano dimensional state and incorporation of dopant into the host lattice. Weak metal sulfur interaction was identified from the FT-IR spectroscopy. The room temperature magnetic studies showed that 10% nickel doped CdS at 10 pH, 11.0 pH and 9.0 pH showed weak ferromagnetic and strong ferromagnetic hysteresis. The variations in the magnetic property of the nanomaterials were caused by the weak interaction of Ni²⁺ with the host material.     

复合絮凝剂APAC处理含镍废水的效果

采用慢速滴碱法制备了复合絮凝剂APAC,研究了处理条件对APAC去除废水中Ni2+及浊度效果的影响,探讨了APAC去除废水中Ni2+和浊度的净化机理.结果表明:APAC对Ni2+有很好的去除能力,去除率最高可达87.42%;废水的pH值越高,Ni2+的去除率越大;APAC中凹凸棒组分在一定程度上促进了Ni2+的去除;当铝与凹凸棒质量比为2:1,盐基度为80%,APAC投加量为32 mg/L,pH值在7～12时,APAC对废水中Ni2+和浊度的去除效果最佳.